Heat resistant oxalate-alkyd-isocyanate cellular plastics



2,698,838 Patented Jan. 4, 1955 United States Patent fifice HEATRESISTANT ()XALAT-E-ALKYD-ISOCY- ANATE. CELLULAR PLASTICS 11 Claims.(Cl. zen-2.5

This invention relates to alkyd resin poly-isocyanate type cellularplastics and relates more particularly to foamedor cellular plasticmaterials of this kind characterized by increased strength and" superiorresistance to distortion-at elevated temperatures.

In our- Letters Patent 2,577,279, issued December 4, 1951, "and filedJune 25, 1948; 2,577,280; issued December 4, 1951, and filed September18, 1948; 2,577,281, issued December 4, 1951, andfiled October 15, 1948,and 2,591,884, issued April 8, 1952, and filed February 17, 1949, and inapplication Serial No. 44,993, filed August 18, 1948, now abandoned, wehave. disclosed alkyd resinpoly-isocyanate plastics in which thecomponent ingredients are simply mixed together, poured into place, andthen allowed to react un' der atmospheric pressure and at roomtemperatures, with or without a post-cure at moderate temperatures, toform low density cellular plastic materials of substantial strength.While the physical strength of our prior materials in relation to theirlow densities was excellent, the materials were not particularlyresistant to heat and tended to distort under load at temperatures inthe region of, say, 200 F. Although this characteristic is not of anyparticular consequence in many applications, there are certain instanceswhere it is highly desirable to employ a low density cellular plasticthat has a higher resistance to distortion at elevated temperatures.

. We have discovered that cellular alkyd resin-diisocyanate plasticshaving superior strength characteristics and materially increasedresistance to distortion at elevated temperatures are obtained where thealkyd resin is an oxalate alkyd resin, that is a resin in which oxalicacid,

. either hydrate or anhydrous, is used directly in the esterificationduring the resin formation. It is, therefore, an object of the presentinvention to provide a high strength, low density alkydresin-diisocyanate reaction product having superior resistance todistortion at increased temperatures characterized by the incorporationtherein of an oxalate alkyd resin.

Another object of the invention is to provide an alkydresin-diisocyanate cellular plastic formulation of the characterdescribed wherein the oxalate alkyd resin is compounded from the oxalicacid and one or more polyhydric alcohols; the oxalic acid and one ormore other dibasic acids and one or more polyhydric alcohols or fromsuch mixtures either oil modified, or not, as desired or as theconditions of intended use dictate. The invention contemplates theemployment of the oxalic acid in the esterification during resinformation, either as the sole dibasic acid or with other dibasic acidsand excellent results have been obtained where dimer acids or dimerizedfatty acids are employed in the resin formulations.

Another object'of the invention is to provide formulations for theproduction of alkyd resin-diisocyanate cellular plastics that mayincorporate'high molecular weight film-forming polymeric"thermoplasticadditives to serve as filmstabilizers during, the foaming reaction toobtain cellular plastic products of superior physical properties. Suchadditives maintain adequate cell-wall rigidity and elasticity during thereaction and yet provide the high plasticity essential to maximumexpansion to eliminate to a large extent cell collapse and therebyassure the formation of strong, low-density foamaceous products. Inaddition to, or instead of the high molecular weight polymericthermoplastic resin additives, one or more appropriate metallic leafingpowders and/or one or more metallic soap powders may be included in thefoam forming reactant mixture to aid in the foaming and cell formingreaction. In situations where his desirable or important to produceflame resistant or self-extinguishing cellular plastic products, flameretardant additives such as allyl esters of aryl phosphonic acids may beincluded in the foam producing reactant mixture. These additives, suchas diallyl 'phenyl phosphonate, bis(methallyl) benzenephosphonate anddiallyl toluene phosphonate, not only render the products flameresistant and decrease flammability, but also materially decrease thedensity of the cellular products which is a totally unexpected functionor proplerty-of the additives in this class of system or materia .Astill further object of the invention is to provide a novelalkyd-resinsuitable for use in the preparation or production of alkydresin-diisocyanate cellular plastic products characterized bythepresence of oxalic acid and by the processingprocedure in producing theresin. Contrary -to the alkyd resin preparation processes of-which Weare aware, we have discovered that the oxalate alkyd resin is mostsuccessfully produced when the oxalic acid is used directly in the alkydresin producing reaction and the reaction is carried out at an initialtemperature of from 180 to 220 F. until the frothing ceases and then thehold or sustained temperature is maintained below 275 F., thetemperature and the time of reaction depending to a considerable degreeupon the speed and efliciency of the agitation of the reactants untilthe desired acid number is obtained.

Other features and advantages of the invention will become apparent fromthe following detailed description of. typical formulations and productsof the invention;

The invention provides, generally, the preparation of an oxalate alkydresin, the mixing of the resin with a diisocyanate with or withoutadditives such as high molecular weight thermoplastic film-formingpolymeric resins, flame retardants, leafing powders, etc. and thesubsequent pouring or application of the resultant reactant'mixture toreact at atmospheric pressure and temperature.

The alkyd resins employed in the reactant resindiisocyanate systems arereactant products of one or more polyhydric alcohols, oxalic acid withor without other dibasic acids, and unmodified or modified with oil andother resins. The resins preferably have an acid number of from 5 to175, a water content of from 0.1% to 5% by weight, and a ratio range ofthe hydroxyl groups to the carboxyl groups in the alkyd reactants of:from 3 bydroxyl (OOH) :1 carboxyl(COOI-I) to 4 hydroxyl (OH) :5carboxyl(COOH). As previously noted, the oxalate alkyd resin may beprepared from oxalic acid and one or more polyhydric alcohols. Examplesof the formulations for such resins are:

While the ratio range of the hydroxyl groups to the carboxyl groups ofthe alkyd resin reactants may be as above described, the above specificoxalate resins 1, 2 and 3 have a ratio of the OH groups to the COOHgroups of their respective alkyd resin reactants of approximately '2 to1 and may have an acid number of from 5 to 175.

7 Examples of the oxalate alkyd resins of the invention preparedfromoxalic acid, other dibasic acids and polyhydric alcohols areas follows,the ratios of the OH groups to the COOH groups of the alkyd resinreactants of the respective resins being indicated:

Resin l-B: Mols Oxalic acid 1 Trimethylol propane 4 v Phthalic anhydride56 Adipic acid l Resin 2-B:

Oxalic acid 1% Trimethylol propane 4 Phthalic anhydride /2 Adipic acid ll2(Ol-I):6 /2(COOH) Resin 3-B:

Oxalic acid 2 Trimethylol. propane 4 Phthalic anhydride /2 Adipic acid 212(OH):9(COOH) Resin 4-B:

Oxalic acid 2 /2 Trimethylol propane 4 Phthalic anhydride 2(OH): 1(COOH)Resin 5-B:

Oxalic acid 1 /2 Trimethylol propane 2% Phthalic anhydride /2 Adipicacid l Pentaerythritol 1 2(OH):1(COOH) Resin 6-B:

Oxalic acid 2 /2 Trimethylol propane 2% Phthalic anhydride /2Pentaerythritol l 2(OH):1(COOH) Resin 7-B:

Oxalic acid 2 Trimethylol propane 4 Phthalic anhydride 1 2(OH):1(COOH)Resin 8-B:

Oxalic acid 2 /2 Trimethylol propane 4 Maleic anhydride /2 The followingrepresent examples of oxalate alkyd resins prepared from oxalic acid andpolyhydric alcohols and 011 modified, the only dibasic acid employedbeing the oxalic acid:

Resin l-C: Mols Oxalic acid 2 Trimethylol propane 4 Dimer acids l Resin2-C:

Oxalic acid 2 /2 Trimethylol propane 4 Dimer acids /2 2(OH):1(COOH)Resin 3-C:

Oxalic acid 2 /2 Trimethylol propane 3% Dimer acids Approx.2(OH):1(COOH) Resin 4-C:

Oxalic acid 2 /2 Trimethylol propane 3 /3 Dimer acids A1 Approx.2(OH):1(COOH) Resin S-C:

Oxalic acid 2 /2 Trimethylol propane 3% Dimer acids A Approx.12(OH):5(COOH) Resin 6C:

Oxalic acid 2 /2 Trimethylol propane 3 Glycerol 1 Dimer acids /2Although the acid numbers of these resins, l to 6C inclusive, may rangebetween 5 and 175, the preferred acid number is between and and thewater content may be between 0.1% and 5% by weight. The amount orproportion of the dimer acids employed in preparing the oxalate alkydresin may vary considerably; for example in the resins of Examples l-Cto 6-C inclusive,

from ,4 to 1 mol of the dimer acids may be used. We have discovered thatresin 3-C when incorporated or employed in the alkyd resin-diisocyanatereactant mixture contributes to the production of exceptionally goodquality, extremely low density cellular plastics. This resin, 3-C, givesgood results where the acid number is from 14 to although this is notnecessarily the limiting acid number range. Resin 5-C has been found tobe practical and altogether effective in the alkyd resin-diisocyanatereactant mixture for producing heat resistant cellular plastics ofsuperior physical strength characteristics.

The following are representative examples of oxalate alkyd resins usefulin the production of the cellular alkyd resin-diisocyanate cellularplastics, the resins of this group being oil modified and prepared fromoxalic acid, one or more additional dibasic acids and one or morepolyhydric alcohols:

Resin 1-D: Mols Oxalic acid 1% Trimethylol propane -2. 3 /2 Phthalicanhydride 3/2 Adipic acid a /2 Pentaerythritol -a /2 Dimer acids /1Approx. 2(OH):1(COOH Resin 2-D:

Oxalic acid 2V2 Trimethylol propane 4 Phthalic anhydride /2 Dimer acidsA3 Approx. 2(OH):1(COOH) Resin 3-D:

Oxalic acid 2 /2 Trimethylol propane 3 Ethylene glycol 1 /2 Maleicanhydride /2 Dimer acids Approx. 2(OH):1(COOH) Resin 4-D:

Oxalic acid 1 /2 Trimethylol propane 2% Phthalic anhydride /2 Adipicacid l Pentaerythritol l Dimer acids ,4,

As in the other oxalate alkyd resin formulations, the acid number mayrange between 5 and 175 with the preferred acid number being between 10and 20 and the dimer acid limits of the resins of this class, l-D to 4-Dinclusive, are from to 1 mol.

In the preparation of the oxalate alkyd resins the component ingredientsare first melted to a fluid condition at a low temperature, for exampleat a temperature below 220 F. The initial esterification reaction iscarried out at a low temperature, for example at a temperature between180 and 220 F. until the frothing ceases, it being our experience thatthe success in preparing the oxalate alkyd resin is the maintenance ofthe relatively low temperatures during the initial and sustainedreaction periods. During the hold or sustained reaction following theinitial frothing reaction the mix is maintained at a temperature of from220 to 275 F. while rapidly agitating the same, this operation beingcontinued until the desired acid number is obtained. While any selectedtype of agitation may be employed, we have found it practical to rapidlystir the reactants with an agitator driven by an electric motor whilebubbling nitrogen, carbon dioxide, or the like, through the mix tomaintain an inert atmosphere. We have observed that the efficiency ofthe agitation or stirring of the reacting mix determines the length oftime required to obtain the desired acid number of the resin and thatwhere the stirring or agitation is more efiicient, a shorter period isrequired to reach the desired acid number. It is to be observed thatwhereas in the customary alkyd resin manufacturing techniques thetemperatures of the mix during the reaction vary between 350 and 550 P.we successfully produce the oxalate alkyd resins with a reactiontemperature in the neighborhood of 275 F. or lower, although we areunable to obtain a satisfactory oxalate alkyd resin by employing thenormal or usual processing temperatures (350 F.).

The dimer acids or dimerized fatty acids included in certain of theabove examples of the oxalated alkyd resins are dimeric polymers ofunsaturated fatty acids such as dimerized linoleic or linolenic acids.These dimer acids may be prepared by heating the methyl esters ofpolyunsaturated acids such as linoleic or linolenic acids at hightemperatures. This may be represented diagrammatically by a Diels-Alderreaction to form the dilinoleic acid (dibasic unsaturated acid) asfollows:

Zinc stearate Aluminum stearate Calcium stearate Magnesium stearateMagnesium hydroxy stearate Barium stearate Zinc laurate Calcium oleateStrontium stearate The proportion of the metallic soap powder used mayrange from A to 7 /2 grams of the selected metallic soap powder or soappowders for each 30 grams of the alky resin. 1

The inclusion of one or more metallic leafing powders in the oxalatealkyd resin-poly isocyanate reactant mixture will result in a cellularplastic product of superior physical properties. Our copendingapplication, Serial No. 44,993, describes the use of such metallicleafing powders in alkyd resin-poly isocyanate reactant mixtures. Themetallic leafing powders must have-the property of leafing whensuspended in a liquid vehicle and when so suspended and applied as apaint have the ability of forming a continuous film on the surface ofthe applied liquid vehicle or paint. we have found to be effective inthe formulations of the invention include:'

Aluminum leafing powder Aluminum bronze leafing Lead leafing powderNickel leafing powder Such metallic leafing powders are employedindividually or in suitable mixtures and in the proportion of from A to7 /2 grams for each 30 grams of the oxalate alkyd resin. Excellentresults have been obtained by employing aluminum leafing powder of suchfineness that not more than 2% is retained on a No. 325 sieve and byemploying aluminum bronze leafing powder, gold bronze leafing powder,and copper bronze leafing powder of such fineness that not more than0.3% is retained on a No. 100 sieve.

Excellent results are obtainable when both a metallic soap powder and ametallic leafing powder are incorporated invthe oxalate alkyd resin-polyisocyanate mixture. Such a combination of fillers appears to ,actsynergistically, that is the combination causes the formation of agreater volume of the cellular plastic than if the same proportionatequantity of each individual filler is used separately in the identicaloxalate alkyd resin-poly isocyanate reactant mixture. When both themetallic leafing powders and the metallic soap powders are used in theformulations of the invention, the metallic leafing powder may beemployed in the proportion of from A to grams for each 30 grams of thealkyd resin and the metallic soap powder may be used inthe proportion offrom hi to 5 grams for each gram of the alkyd resin.

The metallic leafing powders which '6 Flame retardant additives may beadded in the oxalated alkyd resin-poly isocyanate reactant mixture torender the cellular plastic products flame resistant andselfextinguishing when once ignited. The additives efiective for thispurpose are allyl esters of aryl phosphonic acids, namely compoundshaving the general formula where Ar represents aryl and alkarylhydrocarbon radicals and R and R are hydrogen and alkyl hydrocarbonradicals. Compounds of this nature are described in United StatesLetters Patent No. 2,425,765 granted August 19, 1947. Included in thisgroup of compounds are:

1. Diallyl phenyl phosphonate- 2. Bis(methallyl) benzenephosphonate and,

3. Diallyl toluenephosphonate- Quite unexpectedly these additives notonly serve to impart flame resistance to, and to decrease flamepropagation of, the foamed plastic product but also serve to materiallydecrease the density of the foamed material. In practice from 1 gram to20 grams of the additive may be used with each 30 grams of the oxalatealkyd resin. It is usually preferred to employ approximately 5 grams ofthe additive for each 30 grams of the resin.

Other flame proofing and fire retardant agents may be employed insteadof, or in addition to, the unsaturated alkyl esters of aryl phosphonicacids described above. Such agents include tri-chloralkyl phosphates ofthe general formula:

where R1, R2 and R3 are alkyl groups having from 2 to 4 carbon atoms,antimony oxide SbzOs and allyl esters of alkenyl phosphonic acids of theclass described in U. S. Letters Patent No. 2,425,766 issued August 19,1947, namely compounds having the general formula:

R R C:CR PO(OCH2CR:CHR )2 where R, R and R are hydrogen or alkyl and Rand R are hydrogen, alkyl or aryl radicals. Examples of thetrichloralkyl phosphates that are effective in the formulatlons of theinvention are:

Tri-B-chlorethyl phosphate-- and Tri-chloropropyl phosphate- Examples ofthe allyl esters of alkenyl phosphonic acids which we have found to bepractical and effective in the cellular plastic formulations are:

Diallyl isobutene phosphonate and Bis(methallyl) styrene phosphonate Theallyl esters of aryl phosphonic acids, the allyl esters of alkenylphosphonic acids and the tri-chloralkyl phosphates serve to facilitatemixing of the oxalate alkyd resins and the diisocyanate by acting asmutual solvents for both and this tends to avoid premature reactionprior to the final pouring of the reactant mixture. This is important asit permits the utilization of higher water content alkyd resins whichmay be employed when a reduced density foamed plastic product isdesired. The antimony oxide in addition to serving as a fiameproofingagent acts as a cell size regulator so that the cells of the foamedplastic may be of smaller size. The allyl esters of alkenyl phosphonicacids may be used in the proportion of from 1 to 20 grams for each 30grams of the oxalate alkyd resin when employed without the allyl estersof aryl phosphonic acids previously named, and when the allyl esters ofalkenyl phosphonic acids and the allyl esters of aryl phosphonic acidsare both employed their total proportion may be from 1 to 20 grams foreach 30 grams of the oxalate resin. The tri-chloralkyl phosphates may beused in the proportion of from /2 to 10 grams for each 30 grams of thealkyd resin and when used with the allyl esters of aryl phosphonic acidsin the proportion above named, may be employed in the proportion of fromA: to 7 /2 grams for each 30 grams of the alkyd resin. The antimonyoxide may be used in the proportion of from A to grams for each 30 gramsof the alkyd resin with or without the addition of the allyl esters ofaryl phosphonic acids or the trichloralkyl phosphates.

The invention contemplates the inclusion in the reactant mixture of oneor more high molecular weight thermoplastic film-forming polymeric resinadditives which stabilize the foam duringthe reaction, permit the use ofhigher water contents, increase the elasticity of the cell walls duringthe foaming of the reactant mixture and perform other functionsproductive of low density cellular plastics of superior physicalproperties. The resin additives are soluble in meta-toluene diisocyanateand may or may not react therewith. The following resin additives haveeach been found to be practical and efiective in the alkydresin-diisocyanate reactant systems of the invention and when employedin the concentration ranges set forth do not depend for their actionupon the presence of other additives such as'the metallic soap powders,the metallic leafing powders or the flame retardants which latteradditives may or may not be included in the alkyd resin-Ineta-toluenediisocyanate mixture depending upon the intended character of theproducts and their application. In general, a concentration of the highmolecular weight polymeric thermoplastic resin additives ofapproximately 2 grams for each grams of the meta-toluene diisocyanategives excellent results. We have found that for certain specificapplications of the product 2 grams, 4 grams and 6 grams respectively,of the thermoplastic resin additive for each 100 grams of themetal-toluene diisocyanate are valuable in obtaining products of thedesired physical properties and characteristics. It is to be understoodthat the concentrations or proportions of the individual additivesdepend to a considerable extent upon the nature of the additives andthat the concentrations of the additives are somewhat dependant upontheir respective viscosity grades. The film-forming and foam stabilizingresin additives contemplated by the invention include:

Ethyl cellulose Chlorinated natural rubber Benzyl cellulose Naturalrubber Vinyl chloride-vinyl acetate copolymers Polyvinyl chloridePolyvinyl acetate Polystyrene Polydichloro styrene Polymeric acrylateand methacrylate resins and their copolymers Polyvinyl butyral Ethylcellulose, which we have found to be particularly desirable in theformulations of the invention, is a cellulose ether obtained by thereaction of ethyl chloride with alkali cellulose as follows:

where R represents the cellulose radical. From the structure of thenative cellulose H OH ( JHZOH 570 it is seen that each glucose unit hasthree replaceable OH groups, all or some of which may react as above toform the ether linkages. The molecular Weight of ethyl cellulose is highsince a cellulose molecule, having 570 recurring glucose units, has amolecular weight of about 130,000. Very satisfactory results have beenobtained using commercial grades of ethyl cellulose resins wherein thesubstitution values are between 2.15 and 2.60 ethoxyl groups for eachglucose unit, that is where the ethoxyl content is from 43% to 50%. Thepreferred ethoxyl content range of the ethyl cellulose resin is from45.0 to 49.5%. The proportion or concentration of the ethyl cellulose inthe reactant alkyd resin-meta-toluene diisocyanate systems of theinvention is from 0.03 gram to 15 grams of the ethyl cellulose for each100 grams of the meta-toluene diisocyanate, the preferred concentrationof the ethyl cellulose being between /2 to 6 grams for each 100 grams ofthe meta-toluene diisocyanate. Very low concentrations of the ethylcellulose are effective in producing low density foamed plastics havingsmall uniform cells and superior physical characteristics. We believethat the particularly excellent results obtained with only smallconcentrations of the ethyl cellulose are accounted for, at least inpart, by the reaction of the ethyl cellulose with the meta-toluenediisocyanate through addition polymerization between the labile hydrogenatoms of the free (OH) groups in the ethyl cellulose molecules and theisocyanate groups producing soluble,

9 very high molecular weight reactive polyisocyanates. Such a reactionis illustrated as follows:

CH2O C2115 A diethyl cellulose unit in Toluene diisocyanate (excessused) With the extremely low effective concentrations of the ethylcellulose, for example 0.03 gram of the ethyl cellulose resin per 100grams of the meta-toluene diisocyanate, it is evident that there issubstantially no increase in viscosity of the mixture, particularlywhere low viscosity ethyl cellulose is used. The effect of the ethylcellulose is, therefore, not to be ascribed to a viscosity increase butappears to be due to reinforcement and stabilization of the cells of thefoaming reactant mixture preventing collapse of the cells and consequentloss of gas pressure. This is substantiated by the fact that an increasein viscosity of the reactant mixture by dissolving low molecular weightresins, and particularly those that are not predominantly linear such asester gum or glycerol abietate, in the foaming mixture, with the foamstabilizers such as metallic soap, metallic leafing powder, omitted doesnot avoid cell collapse but results in a condition where cell collapsepredominates due to insufficient cell reinforcement so that practicallyno plastic foam volume is obtained. The viscosity of the ethyl celluloseresins which we employ is between 7 and 200 centipoises, and preferablybetween 50 and 100 centipoises, this viscosity being determined from a-by weight concentration of the ethyl cellulose in a solution of from 70to 80 parts by weight of toluene with from 30 to 20 parts by weight ofethanol (denatured 2B ethyl alcohol of 95% strength). A comparison ofthe physical strengths of the cellular plastics prepared fromnon-oxalated alkyd resins and the oxalate resins of theinventiondemonstrates the marked advantages to be gained by employing the oxalateresins in the reactive cellular plastic producing formulationsparticularly where the products may be subjected to elevatedtemperatures. For example, let us consider the formula:

Parts by weight Alykd resin 30 Meta-toluene diisocyanate containing 2%ethyl cellulose of 100 centipoises viscosity and of from 48.0 to 49.5%ethoxyl content Diallyl phenyl phosphonate containing 5% benzoylperoxide where the resin has an acid number of 20 and is compoundedfrom:

Mols Trimethylol propan 4 Adipic acid 2% Phthalic anhydride In actualcompression tests of the reaction product .of this formulation thecompression strengths of the set cured cellular product having a densityof 13 pounds per cubic foot and with the load applied perpendicular 110to the direction of foaming are 475 p. s. i. at 70 F. and 180 p. s. i.at 160 F. However, where the resin employed in this formulation is resin4-B, instead of the above alkyd resin, and the load is applied in thesame manner. to the set cured product the compression strengths are 545p..s. i.'at 70 F. and 300 p. s. i. at 160 F. Again, where resin'S-C issubstituted for the non-oxalate resin in the above formulation the setcured cellular reaction product of ten pounds per cubic foot density hasa compression strength of 238 p. s. i. at 160 F. and a modulus (EX10 of8.7 at 160 F. while a set cured cellular reaction product prepared fromthe non-oxalate resin and having a density of 10 pounds per cubic foothas a compressionstrength of 110 p. s. i. at 160 F. and

15 a modulus (EXl0 of .4 at the same temperature.

The following are typical preferred formulations of the invention, theparts of the components being in parts by weight:

Example A ,o Parts Resin S-C having an acid number of 30 Meta-toluenediisocyanate containing 2% by Weight ethyl cellulose of 100 centipoisesviscosity and having an ethoxyl content of from 45.0% to Diallyl phenylphosphonate containing 5% benzoyl peroxide 5 Example B Parts Resin 5-Chaving an acid number of 20 30 Zinc stearat Diallyl phenyl phosphonatecontaining 5% dissolved benzoyl peroxide 2% Meta-toluene diisocyanatecontaining 2% by weight ethyl cellulose of 100 centipoises viscosity andhaving an ethoxyl content of from 46.8 to 48.5% 20 Example C 7 PartsResin 5C having an acid number of 20 30 Diallyl phenyl phosphonatecontaining 5% by weight dissolved benzoyl peroxide 2% Meta-toluenediisocyanate containing 2% by weight ethyl cellulose having a viscosityof 100 centipoises and having an ethoxyl content of 48 to Example DParts Resin 5-C having an acid number of 20 30 Aluminum leafing powder2% 50 Meta-toluene diisocyanate containing 2% by weight ethyl cellulosehaving a viscosity of 100 centipoises and having an ethoxyl content offrom 46.8

Example E a 7 Parts Resin 5C having an acid number of 20 30 Aluminumleafing powder 2% Diallyl phenyl phosphonate containing 5% by weightdissolved benzoyl peroxide Meta-toluene diisocyanate 17% Example F r I rParts Resin 5-C having an acid number of 10 30 Meta-toluene diisocyanatecontaining 2% by weight ethyl cellulose having a viscosity of 100centipoies and having an ethoxyl content of from 48 to 49.5%--- 20Diallyl phenyl phosphonate containing 5% by weight dissolved benzoylperoxide 2% Example G a a 7 Parts Resin 5-C having an acid number of 1030 7 Meta-toluene diisocyanate containing 2% by weight ethyl cellulosehaving a viscosity of 100 centrpoises and having an ethoxyl content offrom 48 to 49.5% 25 Diallyl phenyl phosphonate containing 5% by weightdissolved benzoyl peroxide 2% Example H Parts Resin 5C having an acidnumber of 10 30 Aluminum leafing powder 2% Meta-toluene diisocyanate. 25

Example I Parts Resin S-C having an acid number of 10 30 Aluminumleafing powder 2 /2 Diallyl phenyl phosphonate containing 5% by weightdissolved benzoyl peroxide 2 /2 Meta-toluene diisocyanate containing 2%by weight ethyl cellulose having a viscosity of 100 centipoises andhaving an ethoxyl content of from 46.8 to 48.5% 20 Example I Parts Resin5-C having an acid number of 15 30 Aluminum leafing powder 5Meta-toluene diisocyanate 20 Antimony oxide 2 /2 Tri-B-chlorethylphosphate 2 /2 Example K Parts Resin 5-C having an acid number of 15 30Aluminum leafing powder 2 /2 Zinc stearate A Meta-toluene diisocyanatecontaining 2% by Weight ethyl cellulose of 100 centipoises viscosity andhaving an ethoxyl content of from 45% to 49% 20 Diallyl phenylphosphonate containing 5% dissolved benzoyl peroxide 2% Example L PartsResin 5-C having an acid number of 20 30 Meta-toluene diisocyanatecontaining 2% by weight ethyl cellulose of 100 centipoises viscosity andhaving an ethoxyl content of from 45 to 49.5% 20 Example M Parts Resin5-C having an acid number of 20 30 Diallyl phenyl phosphonate containing5% dissolved benzoyl peroxide 2 /2 Meta-toluene diisocyanate containing4% by weight ethyl cellulose having a viscosity of 100 centipoises andhaving an ethoxyl content of from 46.8 to 48.5% 15 Example N Parts Resin5-C having an acid number of 20 30 Aluminum leafing powder 1 /2Meta-toluene diisocyanate containing /2% by weight ethyl cellulosehaving a viscosity of 100 centipoises and an ethoxyl content of from 45to 20 Diallyl phenyl phosphonate containing dissolved benzoyl peroxide 5Example 0 Parts Resin 5-C having an acid number of 30 Aluminum leafingpowder 2 /2 Meta-toluene diisocyanate Example P Parts Resin 3C having anacid number of 65 30 Meta-toluene diisocyanate containing 2% by weightethyl cellulose having a viscosity of 100 centipoises and an ethoxylcontent of from 48 to 49.5% 20 Diallyl phenyl phosphonate containing 5%by weight dissolved benzoyl peroxide 5 Example Q Parts Resin 3C havingan acid number of 20 30 Meta-toluene diisocyanate containing 6% byweight ethyl cellulose having a viscosity of 100 centipoises and anethoxyl content of from 48 to 49.5% 20 Antimony oxide 2 /2Tri-B-chlorethyl phosphate 2 /2 12 Example R Parts Resin 1 having anacid number of 60 30 Meta-toluene diisocyanate containing 2% by weightethyl cellulose having a viscosity of centipoises and an ethoxyl contentof from 46.8 to

Example S Parts Resin 4B having an acid number of 100 30 Meta-toluenediisocyanate containing 4% by weight ethyl cellulose having a viscosityof 100 centipoises and an ethoxyl content of from 45 to 49.5% 20Aluminum leafing powder 2 /2 Diallyl phenyl phosphonate containing 5% byweight of dissolved benzoyl peroxide 5 Example T Parts Resin 4B havingan acid number of 25 30 Meta-toluene diisocyanate containing 2% byweight ethyl cellulose having a viscosity of 100 centipoises and havingan ethoxyl content of from 45 to 49.5 20 Antimony oxide 2 /2 Diallylphenyl phosphonate containing 5% by weight of dissolved benzoyl peroxide5 Example U Parts Resin 8-B having an acid number of 50 30 Meta-toluenediisocyanate containing 2% by weight ethyl cellulose having a viscosityof 100 centipoises and having an ethoxyl content of from 45 to 49.5% 20Example V Parts Resin 8-B having an acid number of 30 30 Meta-toluenediisocyanate 20 Zinc stearate 2 /2 Example W Parts Resin 8-B having anacid number of 25 3O Meta-toluene diisocyanate 20 Zinc stearate Aluminumleafing powder 2 /2 Example X Parts Resin l-D having an acid number of75 30 Meta-toluene diisocyanate containing 1% ethyl cellulose having aviscosity of 100 centipoises and having an ethoxyl content of from 45 to49.5 20 Zinc stearate Aluminum leafing powder 2 Diallyl phenylphosphonate containing 5% by In the production of the cellular plasticmaterials or products in accordance with the invention, the selectedingredients are simply mixed together thoroughly in the ratio designedto produce a foamed plastic having the desired density and otherphysical characteristics. The resultant mixture is then poured into themold or cavity in the structure in which it is to form a part or isapplied to a structural surface or the like. The reactant mixture isallowed to react at atmospheric pressure either'with or without theapplication of external heat or attended by a moderate heating of, say,between .120" F. and 150 F. de-

pending upon the size of the hatch, etc. The reaction is allowed to goon to completion to produce the foamed cellular material. Thecellulariiplastic product may then be subjected to a post-cure of fromto 20 hours at a temperature of from 125 F. .to 225 F. to continue thepolymerization of the reaction and thus obtain a stronger and moresolvent resistant material. The plastic firmly and uniformly adheres tothe surfaces of practically any solid material during the foamingreaction and retains its adherence when it has set and cured. As pointedout above, where the cellular plastic products or materials of thisinvention are to be employed in situations where they may be subjectedto elevated temperatures, formulations may be selected which produceproducts that are resistant to heat and remain hard and resistant todistortion at tem peratures of 300 F. or higher. The foamed cellularplastic materials have small cells that are generally spherical inconfiguration and that are non-communicating, the cells being uniformlydistributed throughout the mass.

It should be understood that the invention is not based upon ordependent upon the theories which we have herein expressed. Nor is theinvention to be regarded as limited to the express procedure ormaterials set forth, these details being given only by way ofillustration. We do not regard such specific details as essential to theinvention except insofar as they may be expressed by way of limitationin the following claims, wherein it is our intention to claim allnovelty inherent in the invention as broadly as is permissible in viewof the prior art.v

We claim:

1. The cellular reaction product of an alkyd resin prepared from oxalicacid and a polyhydric alcohol reacted at temperatures below 275 F. tohave an acidnurnber of from 5 to 175 and wherein the hydroxyl groups andcarboxyl groups of the alkyd resin reactants are in the ratio range offrom 3(OH):1(COOH) to 4(OH):5(COOH), from 35 to 150 parts by weight ofmeta-toluene diisocyanate for each 100 parts by weight of said resin,and from .03 part to parts by weight for each 100 parts by weight of themeta-toluene diisocyanate of a film-forming and foam stabilizingthermoplastic resin additive that is soluble in the meta-toluenediisocyanate, selected from the group consisting of:

Ethyl cellulose Polyvinyl acetate Chlorinated natural rubber PolystyreneBenzyl cellulose Polydichloro styrene Natural rubber Polymeric methylmethacryl- Vinyl chloride-vinyl acetate ate copolymers Polyvinyl butyralPolyvinyl chloride 2. The cellular reaction product of an alkyd resinprepared from oxalic acid and a polyhydric alcohol reacted attemperatures below 275 F. to have an acid number of from 5 to 175 andwherein the hydroxyl groups and carboxyl groups of the alkyd resinreactants are in the ratio range of from 3(OH):1(COOH) to 4(OH):5(COOH),from 35 to 150 parts by weight of meta-toluene diisocyanate for each 100parts by weight of said resin and from gram to 7.5 grams for each 30grams of said resin and of metallic leafing powder, selected from thegroup consisting of:

Aluminum leafing powder Lead leafing powder Nickel leafing powder Silverleafing powder Gold leafing powder Copper leafing powder 3. The cellularreaction product of an alkyd resin having a water content of from 0.1%to 5% by weight and reacted at temperatures below 275 F. to have an acidnumber of from 5 to 175 prepared from approximately 2.5 mols oxalicacid, approximately, 3.5 mols trimethylol propane and approximately himol of a dimer of an unsaturated fatty acid selected from the groupconsisting of linoleic and linolenic acids, from 35 to 150 parts byweight of meta-toluene diisocyanate for each 100 parts by weight of saidresin, and from .03 gram to 15 grams for each 100 grams of themeta-toluene diisocyanate of a film-forming and foam stabilizing thermo-1T4 plasticresin additive that is soluble in meta toluene diisocyanate,selected from a group consisting of:

Ethyl cellulose Polyvinyl acetate Chlorinated natural rubber PolystyreneBenzyl cellulose Polydichloro styrene Natural rubber Polymeric methylmethacry- Vinyl chloride-vinyl acetate late copolymers Polyvinyl butyralPolyvinyl chloride v for each 30 grams of said resin of metallic leafingpowder selected from the group consisting of:

Aluminum leafing powder Stainless steel leafing powder Lead leafingpowder Aluminum bronze leafing Nickel leafing powder powder Silverleafing powder Gold bronze leafing powder Gold leafing powder Copperbronze leafing Copper leafing powder powder 5. The cellular reactionproduct of approximately 30 parts of an alkyd resin having a watercontent of from 0.1% to 5% by weight and reacted at temperatures below275" F. to have an acid number of from 5 to 175 prepared from 2.5 --molsoxalic acid, 3% mols trimethylol propane and V 6 mol of a dimer of anunsaturated fatty acid selected from the group consisting of linoleicand linolenic acids, 25 parts of meta-toluene diisocyanate containingfrom 03% to 15% by weight of ethyl cellulose, and 2 /2 parts diallylphenyl phosphonate containing 5% by weight of benzoyl peroxide.

6. The cellular reaction product of approximately 30 parts of an alkydresin having a water content of from 0.1% to 5% by weight and reacted attemperatures below 275 F. to have an acid number of from 5 to 175prepared from 2.5 mols oxalic acid, 3%; mols trimethylol propane and 5mol of a dimer of an unsaturated fatty acid selected from the groupconsisting of linoleic and linolenic acids, 25 parts of meta-toluenediisocyanate containing from .03% to 15% by weight of ethyl cellulose,and 2 /2 parts metallic leafing powder, selected from the groupconsisting of:

Aluminum leafing powder Lead leafing powder Nickel leafing powder Silverleafing powder 7. The cellular reaction product of approximately 30parts of an alkyd resin having a water content of from 0.1% to 5% byweight and reacted at temperatures below 275 F. to have an acid numberof from 5 to 175 prepared from 2.5 mols oxalic acid, 3%; molstrimethylol propane and A mol of a dimer of an unsaturated fatty acidselected from the group consisting of linoleic and linolenic acids, 25parts of meta-toluene diisocyanate containing from .03% to 15% by weightof ethyl cellulose, 2 /2 parts metalflic leafing powder, selected fromthe group consistlng o Aluminum leafing powder Stainless steel leafingpowder Lead leafing powder Aluminum bronze leafing Nickel leafing powderpowder Silver leafing powder Gold bronze leafing powder Gold leafingpowder Copper bronze leafing Copper leafing powder powder and 2 /2 partsdiallyl phenyl phosphonate containing 5% by weight of benzoyl peroxide.

from 35 to parts by weight of meta-toluene diiso- Barium stearatecyanate for each 100 parts by weight of said resin, and from part to 7.5parts for each parts of said resin of metallic soap powder selected fromthe group consisting of:

Zinc stearate Aluminum stearate Calcium stearate Magnesium stearate Zinclaurate Barium stearate Calcium oleate 9. The cellular reaction productof an alkyd resin prepared from oxalic acid and a polyhydric alcoholreacted at temperatures below 275 F. to have an acid number of from 5 to175 and wherein the hydroxyl groups and the carboxyl groups of the alkydreactants are in the ratio range of from 3(OH):1(COOH) to 4(OH) to5(COOH), from to 150 parts by weight of metatoluene diisocyanate foreach parts by weight of said resin, and from to 5 parts by weight ofmetallic soap powder for each 30 parts by weight of said resin selectedfrom the group consisting of:

Zinc stearate Strontium stearate Aluminum stearate Magnesium hydroxideCalcium stearate stearate Magnesium stearate Zinc laurate Calcium oleate10. The cellular reaction product of an alkyd resin prepared from oxalicacid and a polyhydric alcohol reacted at a temperature below 275 F. tohave an acid number of from 5 to 175 and wherein the hydroxyl groups andthe carboxyl groups of the alkyd reactants are in the ratio range offrom 3(OH):1(COOH) to 4(OH) to 5(COOH), from 35 to parts by weight ofmetatoluene diisocyanate for each 100 parts by weight of said resin, andfrom .03 part by weight to 15 parts by weight of ethyl cellulose havingan ethoxyl content of from 45.0

Strontium stearate Magnesium hydroxide stearate 16 to 49.5% for each 100parts by weight of said metatoluene diisocyanate, the ethyl cellulosebeing soluble in the meta-toluene diisocyanate.

11. The cellular reaction product of an alkyd resin prepared from oxalicacid and a polyhydric alcohol reacted at temperatures below 275 F. tohave an acid number of from 5 to and wherein the hydroxyl groups and thecarboxyl groups of the alkyd reactants are in the ratio range of from3(OH):1(COOH) to 4(OH) to 5(COOH), from 35 to 150 parts by weight ofmeta-toluene diisocyanate for each 100 parts by weight of said resin,from .03 part by weight to 15 parts by Weight of ethyl cellulose having"an ethoxyl content of from 45.0 to 49.5 and soluble in the meta-toluenediisocyanate for each 100 parts of the meta-toluene diisocyanate, andfrom 1 to 20 grams for each 30 grams of said resin'of a flame retardantadditive chosen from the group consisting of:

Diallyl phenyl phosphonate Bis (methallyl) benzene phosphonate Diallyltoluene phosphonate Allyl esters of alkenyl phosphonic acids ReferencesCited in the file of this patent UNITED STATES PATENTS 1,108,332Callahan Aug. 25, 1914 1,141,944 Dawson June 8, 1915 1,950,468Zwilgmeyer Mar. 13, 1934 2,111,762 Ellis Mar. 22, 1938 2,491,811 HamDec. 20, 1949 2,498,621 Kropa Feb. 21, 1950 2,529,512 Ott Nov. 14, 19502,577,281 Simon et a1 Dec. 4, 1951 2,591,884 Simon et a1 Apr. 8, 19522,602,783 Simon et a]. July 8, 1952

1. THE CELLULAR REACTION PRODUCT OF AN ALKYD RESIN PREPARED FROM OXALICACID AND A POLYHYDRIC ALCOHOL REACTED AT TEMPERATURES BELOW 275* F. TOHAVE AN ACID NUMBER OF FROM 5 TO 175 AND WHEREIN THE HYDROXYL GROUPS ANDCARBOXYL GROUPS OF THE ALKYD RESIN REACTANTS ARE IN THE RATIO RANGE OFFROM 3(OH):1(OOH) TO 4(OH):5(COOH), FROM 35 TO 150 PARTS BY WEIGHT OFMETA-TOLUENE DIISOCYANATE FOR EACH 100 PARTS BY WEIGHT OF SAID RESIN,AND FROM .03 PART TO 15 PARTS BY WEIGHT FOR EACH 100 PARTS BY WEIGHT OFTHE META-TOLUENE DIISOCYANATE OF A FILM-FORMING AND FOAM STABILIZINGTHERMOPLASTIC RESIN ADDITIVE THAT IS SOLUBLE IN THE META-TOLUENEDIISOCYANATE, SELECTED FROM THE GROUP CONSISTING OF: